SU552023A3 - Method for preparing 3,5-dinitro-4-substitutions of aminophenyl alkyl sulfones - Google Patents

Description

The process can be carried out in an organic solvent medium, for example dimethylformamide. Methp iodide, methyl bromide, methyl chloride are used as alkyl halides; i;

EXAMPLE 1 7.06 g (0.02 mol) of the sodium salt of 3,5-dinitro 4-di-n-propnlaminobenzenesulfinic acid was dissolved in 50 ml of dimethylformamide and 3.2 g added to the prepared solution ( 19.5 ml, 0.024 mol) of methyl iodide. After Q, the reaction mixture is kept at & 0-68 hours at room temperature or, mixed, stirred for 6-8 hours at 40 ° C, or ne | mix for 2 hours in an autoclave at a pressure of $ 1 ,, Then the reaction mass t5 is evaporated in a vacuum of 20-40 mm pi. Art. and the obtained residue is washed with 100-200 ml of hot water, filtered and dried. The result is 5.9-6, 4 g 4.metilsulfonip-2,6-danitro-M; N t n irotshlanilina, yield 85-94%, so pl. Gyulzl enki 20 product 148-151 ° C.

EXAMPLE 2, 7.06 g (0.02 mol) of the sodium salt of 3,5-dinitro-4-dan-propylaminobenzene sulphinic acid is dissolved in 50 ml of dimethylformaLimide and 2.4 g of the prepared solution is added to the prepared solution. 23 (0.022 mol) of ZIL bromide. The reaction mixture is processed by the method described in Example 1, 4.4 to 4.9 g of ethylsulfo1.1-2.6 danitro-N, M-di is prepared in pe :: ulyate. n - prop-shishina yield 60-62%, so pl. the resulting product 147-149 ° C.Zy

PRI me R 3. 7.3 g (0.02 mol) of 3,5-dzio: 1tro-4; jH n - propylaminesbenzene / llochlochloride solution-.

rin in 60 ml of benzene. the solution was added to a pre-prepared solution containing 9.4 g (0.0375 mol) of dry sugar and 35 ml to 3.4 g (0.04 mol) of KHC Jioro sodium carbonate and 60 ml of water, and the mixture was stirred vigorously for 4 -5 hour at low temperatures and 70 ° C. Each hour, i, l g of acidic sodium carbonate is added to the reaction mixture for, dg1, ep: {a} w 40 pH of the reaction mixture is 8-9. Then, the / suspension suspension is evaporated at about 00 mm Hg, Art. until complete removal of the benzene suspension. The residue containing water is extracted with 300 ml of ethyl acetate and, after the solvent has been removed, a sulfinate is obtained. The sulfinate is dissolved in 50 ml of dimethylformamide and after adding 3.2 g (0.0245 mol) of methyl iodide and treating the reaction mass in accordance with the procedure described in the example, 2.8-6.4 g of product are obtained. The output of 4-methylsulfonyl-2,6 - di itro-M,

-di - "- propylaniline | 85-94%, so pl. product 148-15i ° C.

EXAMPLE 4 7.3 g (0.02 mol) of 3,5-din trophdi-n-propylalinobenzenesulfonyl chloride are dissolved in 50 ml of benzene and 3 ml 99 are added to the prepared solution with vigorous stirring. 5% hydrazine hydrate dissolved in a maximum of 40 ml of absolute methyl alcohol. During the addition of the hydrazintadrate solution 60

The pad temperature (# 1 higher than 0.degree. C. After that, the reaction mixture is stirred for 1 hour at room temperature and then allowed to stand overnight. After the addition of Cuml water) and 4 g of sodium hydrogen carbonate hydrazine hydrate is distilled off in a vacuum of 35-40 mm Hg After evaporation of the residue, 100 ml of water was added to the resulting mixture and the mixture was extracted twice with ethyl acetate, using 120 ml of solvent for each extraction. The solvent is separated from the solution containing ethyl acetate, and the desired sulfinate is obtained. The product obtained is dissolved in 50 ml of dimethylformamide and 3.2 g (0.0245 mol) of iodide are added. According to the procedure described in example 1, 5.9-6.4 g of Fmethylsulfo1-ssh-2,6-dinitro-N, N-da-Aj-propylaniline are obtained, yield 85-94%, t. Pl. Received Substances 148-151 ° C.

Example5. 7.3 g (0.02 mol) of 3,5-dinitro4-D1-N-propyl 1 danobenzenesulfonyl chloride is dissolved in 200 ml of acetone. 6.3 g (0.042 mol) of sodium iodide and 3.4 g (0.04 mol) of sodium hydrogen carbonate were added to the prepared solution, the reaction mixture was heated for some time and after evaporation to the residue 100 ml of water were added, 3 g (0.025 mol) of sodium thiosulfate dissolved in 50 ml of water. Mix three times with ethyl acetate using up to 70 ml of solvent for each extract. The solvent is then removed, whereby the desired sulfinate is obtained. The product is dissolved in 50 ml of dimethylformamide. 3.2 g (0.0245 mol) of iodine methyl are added to the solution. The reaction mixture is treated according to the procedure described in Example 1. 5.9-6.4 g 4-megylsul-1Sl-2,6-dinitro-N, Chdi-n-ethyl-ethyl1SH1a is obtained in rezul / lat, yield 85-94% t. pl. the compound obtained.

EXAMPLE 6 Sulfinate is prepared using the procedure described in Example 4. The product is dissolved in 50 ml of dimethylformamide and 2.4 g (0.022 mol) of methyl bromide is added to the prepared solution. The subsequent processing of the reaction mixture is carried out according to the procedure described in Example 1. As a result, 4.4-4.9 g of 4-methylsulfonyl-2,6-dinitro-M, N-di-n-propylaniline are obtained, which corresponds to a yield of 60- 62%, so pl. flaky substance 147-149 ° C.

EXAMPLE 7 The corresponding sulfonium is obtained according to the procedure described in Example 4. The product is dissolved in 50 ml of dimethylformamide and 3 g (0.022 mol) and - butyl bromide are added to the prepared solution. According to the procedure described in Example 1, 4-n-bute; sulfonyl 2, 6-dinitro-M, N-di-n-propylaniline is obtained, yield 70-76%.

Claims (3)

Example 8 Sulfinate was prepared according to the procedure described in Example 5). The product was dissolved in 50 ml of dimethylformamide and 2.4 g (0.022 NiOHb) of ethyl bromide was added to the prepared solution. According to the method described in example 1, 4.4-4.9 g of 4-ethylsulfonyl-2,6-dinitpo-N, N-di-n-hydrochloride aniline are obtained, which corresponds to a yield of 60-62%, t. Pl. of the obtained compound 147-149 ° C. EXAMPLE 9 According to the procedure described in Example 8, 3 g (0.022 mol) of n-butylbromium a are added to the sulfinate, which was dissolved in 50 ml of dimethylformamyl. Using the procedure described in Example I, 1 g of 4-n-butylsulfo-SHL-2,6-dinitro-N, N dk- to propylaniline is obtained, which corresponds to a yield of 70-76%, mp. C, try on. The sulfinate is obtained according to the procedure described in Example 6 and the product is dissolved in 50 ml of dimethylformamide. To the prepared solution was added 2.4 g- (0.022 mol) of pure ethyl. As a result of the operations performed, 4.4-4.9 g of 4-ethylsulphorsyl-2,6-d nitro-M, M-di-c-propylanilipol are obtained, which corresponds to a yield of 60-62%, mp. the resulting product 147-149 C. Example. The sulfinate is obtained according to the procedure described in Example 6 and the product is dissolved in 50 ml of dimethylformamide. To the brtHHOMy solution was added 3 g (0.022 mol) of y-butyl bryumidum. The result is 5-6.1 g of 1 - (- butylsulfonyl-2,6-Dinitro-M, N - di-i-progylaniline, which corresponds to a yield of 7 ° to 76%, mp. Obtained compound 107-108 ° C. The formula of the invention The method according to the beam of 3,5-Edanitro-4-mixed 1x amino phenylsilkyl sulfones of the general formula </ BR> Formulas ЕГ-Ж-НЗ where And, and RI have the indicated equipments; A is an alkali metal atom, subjected to interaction with an alkyl halide of the formula RZ Гйв R has the specified attributes e; Z is a halogen atom, followed by separation of the target product. 2. The method according to claim. Distinguishing from the fact that as alkyl halogen species, iodide 4 e l, methyl bromide, mw l chloride are used as iodide. 3. Method according to paragraphs. 1 and 2, characterized in that the process is carried out in a feed of an organic solvent, preferably in a mixture of ammonium.